CN112757724A - Flexible metal-based graphene electrothermal material and preparation method thereof - Google Patents

Flexible metal-based graphene electrothermal material and preparation method thereof Download PDF

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CN112757724A
CN112757724A CN202011585418.5A CN202011585418A CN112757724A CN 112757724 A CN112757724 A CN 112757724A CN 202011585418 A CN202011585418 A CN 202011585418A CN 112757724 A CN112757724 A CN 112757724A
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flexible
electric heating
graphene
metal
preparation
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CN112757724B (en
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李懿霖
楼美玲
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Hengmai Microelectronics Hangzhou Co ltd
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Ningbo Shiyi Technology Co ltd
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Abstract

本发明涉及电热材料技术领域，尤其涉及一种挠性金属基石墨烯电热材料及其制备方法。一种挠性金属基石墨烯电热材料，包括自上而下依次布设的挠性绝缘层、挠性石墨烯电阻层、挠性绝缘层和金属基板，所述挠性石墨烯电阻层与挠性绝缘层之间还设有压延铜箔，所述电热材料为可弯折的柔性材料，该电热材料能以金属基板为最外层向内弯折直至完全重合叠覆。一种挠性金属基石墨烯电热材料的制备方法，用于生产上述的挠性金属基石墨烯电热材料，包括以下步骤：S1、半固化片成型；S2、制作承印片；S3、丝印制作；S4、叠合。本发明提供了一种可进行折弯、挠曲、电性能稳定的挠性金属基石墨烯电热材料及其制备方法。

Figure 202011585418

The invention relates to the technical field of electrothermal materials, in particular to a flexible metal-based graphene electrothermal material and a preparation method thereof. A flexible metal-based graphene electric heating material, comprising a flexible insulating layer, a flexible graphene resistance layer, a flexible insulating layer and a metal substrate arranged in sequence from top to bottom, the flexible graphene resistance layer and the flexible Rolled copper foil is also arranged between the insulating layers, and the electrothermal material is a flexible material that can be bent, and the electrothermal material can be bent inward with the metal substrate as the outermost layer until it is completely overlapped and overlapped. A preparation method of a flexible metal-based graphene electric heating material, for producing the above-mentioned flexible metal-based graphene electric heating material, comprising the following steps: S1, forming a prepreg; S2, making a printing substrate; S3, making silk screen; S4, superimposed. The invention provides a flexible metal-based graphene electric heating material capable of bending, bending and stable electrical properties and a preparation method thereof.

Figure 202011585418

Description

Flexible metal-based graphene electrothermal material and preparation method thereof
Technical Field
The invention relates to the technical field of electric heating materials, in particular to a flexible metal-based graphene electric heating material and a preparation method thereof.
Background
Currently, graphene electric heating materials can be divided into graphene electric heating substrates in various forms such as a graphene electric heating plate, a graphene electric heating film, and a graphene electric heating cloth. The graphene electric heating plate and the graphene electric heating film are formed by coating graphene slurry on a substrate (such as FR-4 insulating sheets, glass, PET, PI and the like) in a screen printing mode, a gravure printing mode and other modes, arranging electrodes and curing at high temperature to form a thick film resistor, so that a current heat effect is realized, and as shown in figure 1, after AC or DC current passes through the graphene thick film resistor, Joule heat is generated.
The graphene electric heating plate/film starts to appear on the market in 2014, and is mainly applied to heating auxiliary facilities, automobile articles and electronic products, such as wall heating and floor heating for household heating, heating plates for automobile rearview mirrors and automobile batteries, intelligent wearing and the like. The graphene electric heating plate/film is formed by printing graphene conductive slurry on an FR-4 insulating sheet, a PET film, a PI film or glass, and has low heat conductivity and heat dissipation performance and no flexibility. Currently, most companies are primarily developing PTC properties directed at graphene heating sheet/film applications and materials.
However, the current graphene thermal plates/films have some drawbacks:
1. the product is manufactured based on nonmetal, the heat conductivity is low, the heat dissipation coefficient is low, the temperature of the product is uneven, the heat transfer and the heat dissipation are slow, the application scene is limited, and the maximum power density of the current product is 1000 w/square meter.
2. The strength of the product is not enough, the basic characteristic is similar to that of a conventional plastic plate, the bending with small radian can not be carried out, and the bent shape can not be kept after the bending, so that the product design and the shape are not facilitated.
3. The conventional graphene slurry is brittle after being cured, does not have flexibility of multiple bending, and can crack after being bent or flexed for multiple times, so that local resistance is too large after power is supplied, a local burning phenomenon is generated, and a fire risk is easily generated.
4. The conventional electrode can not be bent along with the bending, the risk of separation and layering of the conventional electrode and the insulating layer is easily caused after the conventional electrode is bent, and the conventional copper foil does not have ductility and is easy to break after being bent in a small radian.
In the existing graphene electric heating plate, graphene conductive slurry is printed on an FR-4 insulating sheet, a PET film, a PI film or glass, and then insulation packaging treatment is performed, and the structure is shown in fig. 2.
The graphene conductive paste is printed on an insulating sheet (the general material of the insulating sheet is an FR-4 insulating sheet, a PET insulating sheet, a PI film or glass) through silk-screen printing or gravure printing, and is completely adhered to the insulating sheet through high-temperature curing to form the graphene resistance layer. And then, laminating and packaging the cured composite material of the insulating sheet and the graphene resistance layer with other semi-cured insulating layers to form the stable, sealed and waterproof graphene electric heating plate. Generally, the number of insulating layers N of the upper and lower packages is less than or equal to 3.
However, the technology of combining graphene electrocaloric materials with product modeling is currently in the blank state. Just because the graphene electric heating material has the characteristic of ultra-thin size, for example, the thickness of a conventional graphene electric heating plate is only 0.6-0.8mm, the graphene electric heating material is coupled with the appearance of a product, and the feasibility is achieved. However, the conventional graphene electric heating plate does not have flexibility.
The traditional graphene electric heating plate can realize a stable structure in a plane, but is not suitable for bending and flexing the graphene electric heating plate, and firstly, the graphene electric heating plate is easy to break after being bent or flexed due to the insulating layer base material, cannot keep the bent and flexed shape, and can rebound to the plane shape; secondly, because the graphene resistance layer formed by the traditional graphene slurry after high-temperature curing cannot bear small-radian bending, the small-radian bending can cause the graphene resistance layer to be disconnected, so that great hidden danger is caused, namely, the local resistance is too large, and the heat is concentrated at the position after electrification, so that the burning phenomenon is caused; and thirdly, the electrode of the traditional graphene electric heating plate is made of electrolytic copper foil, has no ductility, cannot bear the tensile stress of bending, and the copper foil is easy to break after bending. For the above reasons, it can be seen that the conventional graphene electric heating plate cannot be bent or flexed, let alone can be shaped along with a curved surface.
Meanwhile, the traditional graphene electric heating plate is slow in heat transfer and heat dissipation, and the insulating layer is generally made of a high polymer material with high thermal resistance and low heat conductivity coefficient, so that the heat of the graphene resistance layer is not easily led out rapidly and dissipated as soon as possible, the service life of the graphene electric heating plate is greatly shortened, and the power density of the graphene electric heating plate is not easily improved.
Therefore, the flexible metal-based graphene electric heating plate can only be used for a planar structure at present and cannot be used for a curved surface modeling structure, the flexible metal-based graphene electric heating plate is developed, short plates which cannot be modeled by the graphene electric heating plate are made up, and the filling of the blank of the subdivision field becomes particularly important.
Disclosure of Invention
The invention aims to provide a flexible metal-based graphene electric heating material which can be bent and flexed and has stable electrical property and a preparation method thereof aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a flexible metal-based graphene electric heating material comprises a flexible insulating layer, a flexible graphene resistance layer, a flexible insulating layer and a metal substrate which are sequentially arranged from top to bottom, wherein a rolled copper foil is further arranged between the flexible graphene resistance layer and the flexible insulating layer, the electric heating material is a bendable flexible material, and the electric heating material can be bent inwards to be completely overlapped by taking the metal substrate as the outermost layer.
According to the invention, the flexible FR-4 prepreg, the flexible graphene conductive paste and the rolled copper foil which are developed by combining the plastic deformation capability of the metal material are utilized to realize the flexible metal-based graphene electric heating plate, so that the curved surface modeling of the base material is realized, and the graphene electric heating material has a wider application platform.
On the basis of the technical scheme, the invention can also adopt the following further technical scheme:
a preparation method of a flexible metal-based graphene electric heating material is used for producing the flexible metal-based graphene electric heating material and comprises the following steps:
s1, molding a prepreg, stirring and dispersing the prepared prepreg glue solution, dipping the prepreg glue solution by a glue dipping machine, drying and rolling to prepare the prepreg;
s2, manufacturing a printing sheet, and cutting the prepreg obtained in the step S1 to obtain the printing sheet;
s3, screen printing, namely adding the printing sheet obtained in the step S2 into graphene conductive paste for screen printing, and drying and curing to obtain a screen printing sheet;
and S4, laminating, namely laminating the printing sheet obtained in the step S2, the silk-screen printing sheet obtained in the step S3 and the metal substrate, trimming, drilling and milling to obtain the electric heating material.
The semi-cured glue solution in the step S1 comprises the following components in percentage by weight:
52 to 60 percent of epoxy resin,
1 to 1.5 percent of dicyandiamide,
0.01 to 0.05 percent of dimethyl imidazole,
17 to 20 percent of dimethylformamide solvent,
KH-5600.15-0.25% of silane coupling agent,
20 to 25 percent of SiO2 superfine silica powder.
The epoxy resin is 430A80 epoxy resin.
And (4) dispersing the glue solution in the step S1 by high-speed stirring, wherein the glue dipping machine adopts a horizontal glue dipping machine or a vertical glue dipping machine.
The step S2 further includes: and (3) carrying out cauterization and lamination treatment on the cut prepreg, and cutting burrs of the treated prepreg.
The graphene conductive paste in the step S3 is canned after ball milling and dispersion treatment to be screen printed, and includes the following components by weight percent:
011A80 epoxy resin 30-35%,
11 to 15 percent of novolac epoxy,
1.5 to 3 percent of 128E epoxy resin,
1.5 to 3 percent of dicyandiamide,
0.01 to 0.05 percent of dimethyl imidazole,
5 to 8 percent of SiO2 superfine silicon powder,
KH-5600.2-0.5% of silane coupling agent,
4 to 7 percent of dimethylformamide solvent,
15 to 22 percent of conductive carbon black,
2.5 to 4 percent of graphene powder,
1.2 to 2 percent of hyperdispersant,
10 to 12 percent of carbitol.
Step S4 further includes roughening the surface of the metal substrate, including the following steps:
s41, carrying out wire drawing treatment on the surface of the metal substrate;
s42, cleaning the metal substrate obtained in the step S41 by high pressure;
s43, oxidizing the metal substrate obtained in step 442;
s44, coating the coupling agent on the surface of the metal substrate obtained in the step S43 and drying.
The drawing roll for the drawing process in the step S41 is 1200 mesh.
The trimming in step S4 is performed by cutting or edge milling.
By adopting the technical scheme of the invention and through polymer technology and process improvement, the invention has the beneficial effects that:
1. the graphene electric heating plate can be bent and flexed, and can keep a designed shape under the action of self plasticity.
2. The graphene electric heating plate can maintain stable electrical performance after being bent and shaped, and cannot generate macroscopic disconnection or hidden fracture of a graphene resistance layer, an insulating layer and an electrode to cause potential safety hazards.
3. The graphene electric heating plate has higher heat-conducting property and heat-radiating property, and is beneficial to improving the design power density of a product and prolonging the service life of the product.
Drawings
Fig. 1 is a schematic structural diagram of a graphene electric hot plate in the background art of a flexible metal-based graphene electric hot material and a preparation method thereof provided by the invention.
Fig. 2 is a structural lamination schematic diagram of a graphene electric heating plate in the background art of a flexible metal-based graphene electric heating material and a preparation method thereof provided by the invention.
Fig. 3 is a schematic structural diagram of a flexible metal-based graphene electric heating plate made of the flexible metal-based graphene electric heating material and the preparation method thereof provided by the invention.
Fig. 4 is a planar diagram of a flexible metal-based graphene electric heating plate made of the flexible metal-based graphene electric heating material and the preparation method thereof provided by the invention.
Fig. 5 is a bending state diagram of a flexible metal-based graphene electric heating plate of the flexible metal-based graphene electric heating material and the preparation method thereof provided by the invention.
FIG. 6 is a flow chart of a flexible metal-based graphene electrothermal material and a preparation method thereof provided by the invention.
The flexible graphene resistor comprises a flexible insulating layer 1, a flexible graphene resistor layer 2, rolled copper foil 3, a flexible insulating layer 4 and a metal substrate 5.
Detailed Description
Specific embodiments of a specific scheme of the flexible metal-based graphene electrothermal material and a preparation method thereof are further described with reference to the accompanying drawings.
In the first embodiment, as shown in fig. 3, a flexible metal-based graphene electrothermal material includes a flexible insulating layer 1, a flexible graphene resistance layer 2, a flexible insulating layer 4, and a metal substrate 5, which are sequentially disposed from top to bottom, and a rolled copper foil 3 is further disposed between the flexible graphene resistance layer 2 and the flexible insulating layer 4.
Specifically, the rolled copper foils 3 are strip-shaped, at least two rolled copper foils are provided, and a certain distance is provided between the two rolled copper foils 3.
In this embodiment, the flexible metal-based graphene electric heating plate is formed by laminating four materials and then forming a functional electric heating material in a vacuum environment at high temperature and high pressure. The functional electrothermal material is shown in fig. 4.
The electric heating material is a bendable flexible material, and can be bent inwards until being completely overlapped by taking the metal substrate 5 as the outermost layer.
However, the strain between the layers of the laminated composite material during bending is different, and a corresponding tensile stress FT or compressive stress FP is generated, as shown in fig. 5. The stress easily causes the phenomena of delamination, fracture, falling off and the like between the layers of the product, thereby causing the failure of the electric heating material. If the electric heating material fails, the risk that the material cannot work or potential safety hazards are generated, so that the flexible electric heating material which is in accordance with safety regulations and does not fail when bent or flexed is challenging to manufacture.
In this embodiment, a plastically deformable metal plate, such as an aluminum/aluminum alloy plate, an iron plate, a copper plate, etc., is used as a base material to ensure that the manufactured electric heating plate has the possibility of plastic deformation and shape retention.
Furthermore, the flexible insulating layer is used for realizing the insulation with the metal base material, so that the product is ensured to meet safety regulations, and simultaneously, the flexible insulating layer can follow the deformation of the metal base material without generating a layering phenomenon. The delamination phenomenon is caused by the fact that the laminated composite material is easy to delaminate and separate due to different strains among layers in the bending process of the laminated composite material, and therefore the laminated composite material fails.
Furthermore, the flexible graphene resistance layer is utilized to follow the deformation of the metal base material and the flexible insulating layer, but the deformation cannot be microscopically broken, so that the electric heating plate cannot be subjected to local overheating failure at the turning position.
Furthermore, the rolled copper foil is deformed along with the deformation of other materials, so that the electrode is prevented from being broken and failure in power failure is avoided.
In a second embodiment, in order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, a specific FR-4 prepreg glue solution is configured, where the glue solution includes the following components in percentage by weight:
52 percent of epoxy resin,
1 percent of dicyandiamide,
0.01 percent of dimethyl imidazole,
17 percent of dimethylformamide solvent,
KH-5600.15% of silane coupling agent,
25 percent of SiO2 superfine silicon powder,
4.84 percent of water.
Wherein the CAS number of the epoxy resin is 61788-97-4, the CAS number of the dicyandiamide is 461-58-5, the CAS number of the dimethylimidazole is 693-98-1, the CAS number of the dimethylformamide is 68-12-2, the CAS number of the silane coupling agent KH-560 is 2530-83-5-8, and the CAS number of the SiO2 is 14808-60-7.
After the glue solution prepared by the formula is prepared, uniformly coating the glue solution on 7628 glass fiber cloth through a vertical gluing machine, and drying to prepare a prepreg for subsequent lamination. The rest is the same as the first embodiment.
In a third embodiment, in order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, a specific FR-4 prepreg glue solution is configured, where the glue solution includes the following components in percentage by weight:
60 percent of epoxy resin,
1.5 percent of dicyandiamide,
0.05 percent of dimethyl imidazole,
18 percent of dimethylformamide solvent,
KH-5600.25% of silane coupling agent,
SiO2 superfine silica powder 20.2%.
After the glue solution prepared by the formula is prepared, uniformly coating the glue solution on 7628 glass fiber cloth through a vertical gluing machine, and drying to prepare a prepreg for subsequent lamination. The rest is the same as the first embodiment.
In order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, a specific FR-4 prepreg glue solution is configured, where the glue solution includes the following components in percentage by weight:
57 percent of epoxy resin,
1.2 percent of dicyandiamide,
0.04 percent of dimethyl imidazole,
18 percent of dimethylformamide solvent,
KH-5600.2% of silane coupling agent,
23.56 percent of SiO2 superfine silica powder.
After the glue solution prepared by the formula is prepared, uniformly coating the glue solution on 7628 glass fiber cloth through a vertical gluing machine, and drying to prepare a prepreg for subsequent lamination. The rest is the same as the first embodiment.
In a fifth embodiment, in order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, a specific graphene conductive paste is configured, and the paste comprises the following components in percentage by weight:
011A80 epoxy resin 30 percent,
11 percent of phenolic aldehyde epoxy resin,
1.5 percent of 128E epoxy resin,
1.5 percent of dicyandiamide,
0.01 percent of dimethyl imidazole,
5 percent of SiO2 superfine silicon powder,
KH-5600.2% of silane coupling agent,
4 percent of dimethylformamide solvent,
15 percent of conductive carbon black,
2.5 percent of graphene powder,
1.2 percent of hyperdispersant,
10 percent of carbitol,
and (4) 18.09 percent of water.
After the conductive ink is prepared by the formula, the conductive ink is ground by a ball mill for later use. The rest is the same as the first embodiment.
In a sixth embodiment, in order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, a specific graphene conductive paste is configured, and the paste comprises the following components in percentage by weight:
011A80 epoxy resin 35%,
15 percent of phenolic aldehyde epoxy resin,
3 percent of 128E epoxy resin,
3 percent of dicyandiamide,
0.05 percent of dimethyl imidazole,
8 percent of SiO2 superfine silicon powder,
KH-5600.5% of silane coupling agent,
7 percent of dimethylformamide solvent,
22 percent of conductive carbon black,
4 percent of graphene powder,
2 percent of hyperdispersant agent,
0.45 percent of carbitol.
After the conductive ink is prepared by the formula, the conductive ink is ground by a ball mill for later use. The rest is the same as the first embodiment.
Seventh embodiment, in order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, a specific graphene conductive paste is configured, and the paste comprises the following components in percentage by weight:
011A80 epoxy resin 33 percent,
13 percent of BPA-novolec modified epoxy,
2.9 percent of 128E epoxy resin,
2 percent of dicyandiamide,
0.03 percent of dimethyl imidazole,
6.9 percent of SiO2 superfine silicon powder,
KH-5600.3% of silane coupling agent,
5 percent of dimethylformamide solvent,
20 percent of conductive carbon black,
3.4 percent of graphene powder,
1.7 percent of hyperdispersant,
carbitol 11.77%.
After the conductive ink is prepared by the formula, the conductive ink is ground by a ball mill for later use. The rest is the same as the first embodiment.
In an eighth embodiment, in order to prepare the flexible metal-based graphene electrothermal material in the first embodiment, the surface of the metal substrate needs to be roughened, and the roughening process includes: drawing wire, oxidizing, coating coupling agent and drying. The wire drawing roller is 1200 meshes, wire drawing is carried out by a high-speed roller brush, then oxidation is carried out after high-pressure cleaning, and the intermolecular binding force is improved through coating of a coupling agent, so that the metal substrate and the prepreg can be perfectly bonded to form a whole. The rest is the same as the first embodiment.
In a ninth embodiment, as shown in fig. 5, a method for preparing a flexible metal-based graphene electrothermal material is used for producing the flexible metal-based graphene electrothermal material, and includes the following steps:
s1, molding a prepreg, stirring and dispersing the prepared prepreg glue solution, dipping the prepreg glue solution by a glue dipping machine, drying and rolling to prepare the prepreg;
s2, manufacturing a printing sheet, cutting the prepreg obtained in the step S1, baking and laminating the cut prepreg, and cutting burrs of the processed prepreg to obtain the printing sheet;
s3, screen printing, namely adding the printing sheet obtained in the step S2 into graphene conductive paste for screen printing, and drying and curing to obtain a screen printing sheet;
and S4, laminating, namely laminating the printing sheet obtained in the step S2, the silk-screen printing sheet obtained in the step S3 and the metal substrate, trimming, drilling and milling to obtain the electric heating material.
The graphene electric heating plate realized by the preparation scheme has the characteristics of flexibility and flexibility, can realize the curved surface modeling and the capability of maintaining the designed shape according to the requirements of designers, and has wider application space.
Further, the graphene electric heating plate realized by the embodiment has higher heat transfer capacity and heat dissipation capacity, can break through the limitation that the power density of the traditional graphene electric heating plate is about 1000 w/square meter, and directly improves the power density to 2000 w/square meter without influencing the service life of the product.
Furthermore, the graphene electric heating plate realized by the embodiment has higher heat conduction and heat dissipation capability, and due to the flame-retardant nature of metal and the special formula of the high polymer material, the product has better flame-retardant effect, can break through the limitation that the traditional graphene electric heating plate can only be in UL94V0 within the plastic flame-retardant certification range, directly reaches the fireproof A1 grade, and is safer and more reliable in application in home and buildings.
Further, the graphene electric heating plate realized by the embodiment can enable the temperature of the plate surface to be more uniform due to the improvement of the heat conduction performance in the plane, and meanwhile, the burning phenomenon of the traditional graphene electric heating plate due to overhigh local temperature can be avoided.
Further, the graphene electric hot plate realized by the embodiment can better improve the surface hardness and perform surface coloring treatment by utilizing the current metal surface treatment process and coloring process due to the adhesion of the surface metal layer, so that the characteristics of scratch resistance, scratch resistance and permanent non-discoloration of the surface are achieved, and meanwhile, the surface treatment cost can be greatly reduced.
It is to be noted that the foregoing is only illustrative of the preferred embodiments of the present invention and the technical principles employed. It will be understood by those skilled in the art that the present invention is not limited to the particular embodiments described herein, but is capable of various obvious changes, rearrangements and substitutions as will now become apparent to those skilled in the art without departing from the scope of the invention. Therefore, although the present invention has been described in greater detail by the above embodiments, the present invention is not limited to the above embodiments, and may include other equivalent embodiments without departing from the spirit of the present invention, and the scope of the present invention is determined by the scope of the appended claims.

Claims (9)

1.一种挠性金属基石墨烯电热材料，其特征在于包括自上而下依次布设的挠性绝缘层、挠性石墨烯电阻层、挠性绝缘层和金属基板，所述挠性石墨烯电阻层与挠性绝缘层之间还设有压延铜箔，所述电热材料为可弯折的柔性材料，该电热材料能以金属基板为最外层向内弯折直至完全重合叠覆。1. a flexible metal-based graphene electric heating material is characterized in that comprising a flexible insulating layer, a flexible graphene resistance layer, a flexible insulating layer and a metal substrate arranged successively from top to bottom, the flexible graphene A rolled copper foil is also arranged between the resistance layer and the flexible insulating layer. The electrothermal material is a flexible material that can be bent. The electrothermal material can be bent inward with the metal substrate as the outermost layer until it is completely overlapped. 2.一种挠性金属基石墨烯电热材料的制备方法，其特征在于用于生产如权利要求1所述的挠性金属基石墨烯电热材料，包括以下步骤：2. a preparation method of flexible metal-based graphene electric heating material, is characterized in that being used for producing the flexible metal-based graphene electric heating material as claimed in claim 1, comprises the following steps: S1、半固化片成型，将半固化胶液配置好之后进行搅拌分散，通过浸胶机浸胶后烘干收卷，制成半固化片；S1. The prepreg is formed, the prepreg is made by stirring and dispersing the prepreg after dipping the prepreg, and drying and winding after dipping with a dipping machine; S2、制作承印片，将步骤S1所得的半固化片进行裁切得到承印片；S2, making a printing plate, and cutting the prepreg obtained in step S1 to obtain a printing plate; S3、丝印制作，将步骤S2所得的承印片加入石墨烯导电浆料进行丝网印刷，完成之后进行烘干固化制得丝印片；S3, screen printing production, adding the printing substrate obtained in step S2 to the graphene conductive paste for screen printing, and drying and curing after completion to obtain a screen printing sheet; S4、叠合，将步骤S2所得的承印片、步骤S3所得的丝印片和金属基板进行叠合并层压，进行修整和钻铣后制得电热材料。S4. Lamination, superimposing and laminating the printing substrate obtained in step S2, the silk screen printing sheet obtained in step S3 and the metal substrate, trimming, drilling and milling to obtain an electrothermal material. 3.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S1中的半固化胶液包括以下重量百分比的组分：3. the preparation method of a kind of flexible metal-based graphene electric heating material according to claim 2, is characterized in that the semi-cured glue liquid in described step S1 comprises the following components by weight: 环氧树脂52％～60％，Epoxy resin 52%～60%, 双氰胺1％～1.5％，Dicyandiamide 1%～1.5%, 二甲基咪唑0.01％～0.05％，Dimethylimidazole 0.01%～0.05%, 二甲基甲酰胺溶剂17％～20％，Dimethyl formamide solvent 17% to 20%, 硅烷偶联剂KH-560 0.15％～0.25％，Silane coupling agent KH-560 0.15%～0.25%, SiO2超细硅微粉20％～25％。SiO2 ultra-fine silicon powder 20% to 25%. 4.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S1中胶液通过高速搅拌分散，所述浸胶机采用卧式浸胶机、或立式浸胶机。4. the preparation method of a kind of flexible metal-based graphene electric heating material according to claim 2, is characterized in that in described step S1, glue solution is dispersed by high-speed stirring, and described dipping machine adopts horizontal dipping machine, Or vertical dipping machine. 5.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S2还包括：将裁切后的半固化片进行烙固和层压处理，并将处理后的半固化片进行毛边的裁剪。5. the preparation method of a kind of flexible metal-based graphene electric heating material according to claim 2, it is characterized in that described step S2 also comprises: the prepreg after cutting is carried out ironing and lamination processing, and processing After the prepreg for cutting the burrs. 6.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S3中的石墨烯导电浆经过球磨分散处理后进行罐装以待丝网印刷，该石墨烯导电浆包括以下重量百分比的组分：6. the preparation method of a kind of flexible metal-based graphene electric heating material according to claim 2, it is characterized in that the graphene conductive paste in described step S3 carries out canning to wait for screen printing after ball milling dispersion treatment, The graphene conductive paste includes the following components by weight: 011A80环氧树脂30％～35％，011A80 epoxy resin 30%～35%, 酚醛环氧11％～15％，Novolac epoxy 11% to 15%, 128E环氧树脂1.5％～3％，128E epoxy resin 1.5%～3%, 双氰胺1.5％～3％，Dicyandiamide 1.5%～3%, 二甲基咪唑0.01％～0.05％，Dimethylimidazole 0.01%～0.05%, SiO2超细硅微粉5％～8％，SiO2 ultra-fine silicon powder 5% to 8%, 硅烷偶联剂KH-560 0.2％～0.5％，Silane coupling agent KH-560 0.2%～0.5%, 二甲基甲酰胺溶剂4％～7％，Dimethylformamide solvent 4% to 7%, 导电炭黑15％～22％，Conductive carbon black 15% to 22%, 石墨烯粉体2.5％～4％，Graphene powder 2.5% to 4%, 超分散剂1.2％～2％，Hyperdispersant 1.2%～2%, 卡必醇10％～12％。Carbitol 10% to 12%. 7.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S4还包括金属基板表面进行粗化处理，包括以下步骤：7. the preparation method of a kind of flexible metal-based graphene electrothermal material according to claim 2, is characterized in that described step S4 also comprises metal substrate surface roughening treatment, comprises the following steps: S41、将金属基板表面进行拉丝处理；S41, performing wire drawing processing on the surface of the metal substrate; S42、将步骤S41所得的金属基板通过高压清洗；S42, cleaning the metal substrate obtained in step S41 by high pressure; S43、将步骤442所得的金属基板进行氧化处理；S43, performing oxidation treatment on the metal substrate obtained in step 442; S44、将步骤S43所得的金属基板表面涂覆偶联剂并烘干。S44, coating the surface of the metal substrate obtained in step S43 with a coupling agent and drying. 8.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S41中拉丝处理的拉丝辊为800目～1500目。8 . The method for preparing a flexible metal-based graphene electrothermal material according to claim 2 , wherein the drawing rollers for wire drawing in the step S41 are 800 meshes to 1500 meshes. 9 . 9.根据权利要求2所述的一种挠性金属基石墨烯电热材料的制备方法，其特征在于所述步骤S4中的修整采用裁切或铣边进行。9. The preparation method of a flexible metal-based graphene electrothermal material according to claim 2, wherein the trimming in the step S4 is performed by cutting or edge milling.
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